Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/327—Macromolecular coupling substances
  • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/132—Anti-ultraviolet fading
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/158—Development inhibitor releaser, DIR
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/16—Blocked developers

Definitions

• the present invention relates to a latex of copolymer containing recurring units including a group useful in silver halide photography and recurring units including a strong hydrophilic group, and to photographic silver halide emulsion materials containing such latex.
• latexes may contain a high percentage of polymer particles e.g. up to 50 % by weight, and nevertheless still possess a relatively low viscosity.
• polymer particles e.g. up to 50 % by weight
• these latexes there can be dispensed with the use of organic solvents or alkaline solutions as well as with special dispersing techniques.
• latexes are not without problems of e.g. dispersion stability and may give rise to a lower activity of the photographically useful group since the latter is incorporated in the polymer structure of a dispersed particle.
• An improved dispersion stability can be obtained by incorporating an amount of emulsifying agent in the latex but such often at the expense of undesired foaming and the occurrence of coating defects of layers incorporating such latexes such as streaks and repellency spots.
• the present invention provides an aqueous highly stable dispersion of a copolymer (also called copolymer latex), the copolymer containing recurring units of a monomer which includes a photographically useful group, that plays a chemical role in the preparation, storage and/or processing of a photographic silver halide emulsion material or defines thereof at least partly the spectral absorption characteristics, and recurring units of an ionogenic surface active monomer, characterized in that the said ionogenic surface active monomer corresponds to the formula (A) : wherein :
• the stability of the copolymer latices according to the invention is ensured by the combined presence in the ionogenic comonomer of at least one long hydrophobic group containing at least 8 carbon atoms, and of a strong hydrophilic group formed by the sulfonic acid, sulfuric acid or phosphonic acid group or salt thereof.
• the particles in the latices according to the invention usually have an average diameter below 100 nm, in most cases substantially below 70 nm so that the latices are excellently compatible with coating compositions comprising hydrophilic colloids, such as gelatin. Layers applied from a mixture of the latices with gelatin coating compositions are completely clear and transparent after drying. Probably the average small diameter of the latex particles is due to a better micelle-formation.
• the sodium salt of the acrylamidostearic acid was formed by adding an equivalent amount of sodium hydroxide dissolved in methanol, followed by freeze-drying.
• the above carboxylic acid was dissolved in methanol, and there was added thereto an excess of sodium hydroxide dissolved in methanol. Yield : 37 g of the sodium salt.
• the sodium salt of 9(10)-acrylamidostearyl sulphate was prepared as described in US Patent Specification 3,640,922, Example 7.
• the particle size of the emulsion copolymer formed depends on the content of ionogenic comonomer present in the copolymer. Polymer particles having an average diameter smaller than 100 nm, in most cases smaller than 70 nm, are obtained when the copolymer comprises between 2 and 10 % by weight of the ionogenic comonomer.
• the photographically useful group present in one of the said monomers is a group that plays a chemical role in the preparation, storage and/or processing of a photographic silver halide emulsion material, or defines thereof at least partly the spectral absorption characteristics.
• such a group may function as a colour coupler, a competing coupler, a development accelerator e.g. benzyl- ⁇ -picolinium bromide, a foggant including hydrazines and hydrazides e.g. acetyl-phenylhydrazine, a developing agent e.g. a hydroquinone, a 1-phenyl-3-pyrazolidinone, ascorbic acid and the like, a fog-inhibiting compound e.g.
• a development accelerator e.g. benzyl- ⁇ -picolinium bromide
• a foggant including hydrazines and hydrazides e.g. acetyl-phenylhydrazine
• a developing agent e.g. a hydroquinone, a 1-phenyl-3-pyrazolidinone, ascorbic acid and the like
• a fog-inhibiting compound e.g.
• a 1-phenyl-5-mercaptotetrazole a development inhibitor releasing compound (DIR-compound), a bleaching-inhibitor-releasing compound (BIR-compound), a bleaching-activator-releasing compound (BAR-compound), a dye e.g. serving for filter purposes or an ultra-violet light absorbing compound.
• DIR-compound development inhibitor releasing compound
• BIR-compound bleaching-inhibitor-releasing compound
• BAR-compound bleaching-activator-releasing compound
• a dye e.g. serving for filter purposes or an ultra-violet light absorbing compound.
• one or more monomers which include a photographically useful group may be used.
• the invention is particularly concerned with copolymer latices wherein the recurring units of the monomer which includes a photographically useful group are recurring units of a monomeric coupler which is capable of oxidatively coupling with colour developing agents to form dyes or colourless compounds i.e. units of a monomeric colour coupler and/or a monomeric competing coupler.
• Competing couplers are well-known couplers used in colour photography in those instances where oxidation products of colour developing agents should be rendered ineffective for preventing degradation of the image quality.
• the ethylenically unsaturated photographic colour coupler monomers or competing coupler monomers used in the formation of copolymer latexes of the present invention are generally of the type represented by the following general formula (B) : wherein :
• the colour coupler or competing coupler group Q may be e.a.
• Examples of monomeric colour couplers suitable for copolymerization to form a latex copolymer according to the present invention can be found e.g. in the Belgian Patent Specifications 584,494; 602,516, and 669,971, in the United Kingdom Patent Specifications 967,503; 1,130,581; 1,247,688; 1,269,355; 1,363,230; and in the U.S.Patent Specification 3,356,686.
• monomeric colour couplers and competing couplers are :
• the monomers including a photographically useful group which are used in the formation of a copolymer latex according to the present invention can further be monomers including a UV-absorbing moiety.
• UV-absorbing hydrophobic compounds that can be transformed into ethylenically unsaturated monomers are e.g. of the type described in the United States Patent Specifications 2,739,888; 3,468,897; 3,652,284; 3,687,671 and 3,706,700.
• the monomer including a photographically useful group can be a monomeric DIR-compound, BIR-compound, and BAR-compound formed from a known DIR-, BIR- and BAR-compound by introduction of an ethylenically unsaturated group.
• DIR-, BIR- and BAR-compounds are well known in the art and are compounds which by an elimination reaction during photographic processing release a development inhibitor, bleach inhibitor or bleach accelerator. These compounds include the well-known classes of couplers e.g. as-referred to hereinbefore, which carry at their coupling position a group which upon being split off by reaction of the coupler with oxidized developing agent, forms a development inhibitor, bleach inhibitor or bleach accelerator.
• DIR-compounds are described by Barr et al in Photographic Science and Engineering Vol. 13, no. 2, March-April 1969 p. 74-80, and ibidem no. 4, July-August 1969, p. 214-217, in the United States Patent Specifications 3,148,062; 3,227,554; 3,617,291 and the published German Patent Application DE-OS 2,414,006.
• BIR-compounds are described e.g. in the United States Patent Specifications 3,705,799 and 3,705,803 and the published German Patent Applications DE-OS 2,405,279; 2,412,078 and 2,412,610.
• bleach inhibitor releasing compounds for use with silver halide emulsion layers are compounds releasing a bleach inhibitor upon alkaline development in the areas where the silver image is formed. Such compounds are described e.g. in the United States Patent Specification 3,705,801.
• the BAR-compounds may be of the same type as described hereinbefore for the BIR-compounds with the difference that the image-wise releasable bleach inhibitor moiety is now a bleach accelerator moiety.
• the image-wise releasable bleach inhibitor moiety is now a bleach accelerator moiety.
• the polymeric compounds e.g. couplers according to the present invention can be characterized by their so-called equivalent molecular weight.
• equivalent molecular weight is understood the number of grams of polymer containing 1 mole of polymerized monomeric compound with photographically useful group e.g. monomeric coupler. It can be compared with the molecular weight of the non-polymeric classical non-migratory photographically useful compound e.g. coupler.
• the equivalent molecular weight of polymeric latex compounds according to the invention can vary within very wide limits, preferably from 200 to 2000.
• the latices of the present invention can be prepared by emulsion polymerisation using a polymerisation initiator as described e.g. in the United States Patent Specification 3,926,436, Belgian Patent Specification 669,971 and United Kingdom Patent Specification 1,130,581.
• polymerization initiators suitable for use in the above emulsion polymerisation process are e.g. persulphates such as ammonium and potassium persulphate, azonitrile compounds such as 4,4'-azo-bis(4-cyanovaleric acid) and likewise peroxide compounds e.g. benzoylperoxide.
• persulphates such as ammonium and potassium persulphate
• azonitrile compounds such as 4,4'-azo-bis(4-cyanovaleric acid)
• peroxide compounds e.g. benzoylperoxide.
• the aqueous dispersion of the present polymer particles i.e. the latex of the present invention may contain optionally conventional emulsifiers although they can be omitted. If used, they can usually be employed in smaller proportion than is possible with known procedures where no monomeric surfactant in the copolymerisation is used.
• the monomeric surfactants according to general formula (A) provides in a 1 % by weight aqueous solution a tensio-activity which results in an air/water surface tension lower than 40 mN/m at 20°C.
• the latex polymer of the present invention may comprise and usually does comprise still other repeating units that are colourless and are chemically inert in the preparation, storage and processing of a photographic silver halide emulsion material.
• These repeating units are derived from a monomer or mixture of monomers providing particular physical characteristics to the latex e.g. improved thermal stability, and improved compatibility with photographic binders e.g. gelatin.
• Colourless ethylenically unsaturated monomers that are chemically inert in the sense as defined and that are copolymerisable with the monomers according to general formula (A) and the monomers containing a photographically useful group are e.g. : acrylic acid, methacrylic acid and esters and amides derived from these acids, ⁇ -chloroacrylic acid, ⁇ -alkacrylic acids, wherein the substituting alkyl contains from 1 to 4 carbon atoms e.g.
• esters and amides derived from acrylic acid, ⁇ -chloroacrylic acid and these ⁇ -alkacrylic acids such as acrylamide, methacrylamide, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate
• vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate
• aromatic vinyl compounds and derivatives thereof such as styrene and its derivatives, e.g.
• vinyl toluene vinyl acetophenone and sulphostyrene, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers such as vinyl ethyl ether, maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridines e.g. 2- and 4-vinyl-pyridine and ethylenically unsaturated monomers such as 2-acetoacetoxyethylmethacrylate.
• the latices containing the functional copolymer particles as specified above and prepared according to the known emulsion polymerization processes can be loaded with hydrophobic functional substances as described in the United Kingdom Patent Specifications 1,504,949 and 1,504,950 and the published German Patent Specification (DE-OS 2,835,856) e.g. accomplished by gradually adding the latex to a stirred solution of a hydrophobic substance to be loaded onto and/or into the latex particles in a water-miscible organic solvent or in a mixture of such solvents to such an extent that the hydrophobic substance becomes insoluble in the diluted solvent and optionally removing the organic solvent(s) at least partially from the latex.
• hydrophobic functional substances as described in the United Kingdom Patent Specifications 1,504,949 and 1,504,950 and the published German Patent Specification (DE-OS 2,835,856) e.g. accomplished by gradually adding the latex to a stirred solution of a hydrophobic substance to be loaded onto and/or into the latex particles in a water-m
• hydrophobic organic functional substances can be loaded on the present latex copolymer particles.
• Hydrophobic substances suitable for loading are e.g. hydrophobic colour couplers, hydrophobic competing couplers, hydrophobic development-inhibitor-releasing compounds, hydrophobic W-absorbing compounds, hydrophobic filter dyes, hydrophobic sensitizing agents, hydrophobic colour developing agents, hydrophobic black-and-white silver halide developing agents, hydrophobic development-activator-releasing compounds, hydrophobic bleaching-inhibitor-releasing compounds, hydrophobic optical brightening agents, hydrophobic anti-oxidizing agents, hydrophobic silver halide solvents, or hydrophobic dye-releasing agents and mixtures thereof.
• the hydrophobic "loading" substances may have a function similar and consequently additive to that of the photographically useful units of the copolymer latex particles themselves.
• the copolymer latex particles may have recurring units with a colour coupler function and the loaded hydrophobic substance is a colour coupler as well, so that by the combined colour coupler action an increased colour density can be obtained.
• the function of recurring units of the copolymer latex particles and the loaded hydrophobic substance may be different as well.
• the copolymer particles may comprise recurring units having a colour coupler function
• the loaded hydrophobic substance has e.g. a competing coupler function, a DIR-function, an UV-absorbing function, an anti-fogging function or developing function.
• Suitable water-miscible organic solvents for hydrophobic substance to be loaded are acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, and N-methyl- pyrolidone. Mixtures of two or more of these solvents can be used likewise.
• the reaction mixture was stirred and for a while the temperature dropped to 90°C whereupon it rose again to 95-96°C after the polymerisation started. As soon as that temperature was reached an amount of initiator solution and another fifth of the above mixture of monomers (A), (B) and (C) as described above was introduced into the reaction flask. After a drop of the temperature to 90°C heat was supplied to reach again 96°C. The above procedure of stepwise addition of initiator solution and monomers was repeated thrice again. After the last addition the contents of the reaction flask were heated for 45 min at reflux temperature. The obtained latex was cooled to 20°C and filtered. Yield : 570 ml of latex. Concentration of the copolymer in the latex : 16.4 g per 100 ml. Equivalent molecular weight : 402. Average particle size : 75 nm.
• the preparation of the copolymer was carried out as described in Preparation I with the difference, however, that 5 g of the sodium salt of N-allyl, N[2'(sulphobutyl)] octadecanoylamide were used instead of 5 g of monomer (A). Yield : 477 g of latex. Concentration of the copolymer in the latex : 18.6 g per 100 ml. Equivalent molecular weight : 369. Average particle size : 72 nm.
• Latex of the copolymer of N[1-phenyl- ⁇ 2-pyrazolin-5- one-yl(3')methacrylamide, butylacrylate and the sodium salt of ⁇ -sulphopalmitic acid allylester having the following structural formula :
• the preparation of the copolymer was carried out as described in Preparation I with the difference, however, that 5 g of the sodium salt of ⁇ -sulphopalmitic acid allylester were used instead of monomer (A). Yield : 592 g of latex. Concentration of the copolymer in the latex : 15.6 g per 100 ml. Equivalent molecular weight : 392. Average particle size : 79 nm.
• the preparation was carried out analogously to preparation I but using the following monomer mixture : 40 g of N[3-hydroxy-4(1',1',2',2',3',3',3'-heptafluoro- butyrylamino)phenyl]methacrylamide, 5 g of the sodium salt of 2-acrylamido hexadecane sulphonic acid in 200 ml of demineralised water, 45 g of ethyl acrylate and 10 g of methacrylic acid, the latter two monomers being liquids at room temperature. Yield : 554 ml of latex. Concentration of the copolymer in the latex : 16.2 g per 100 ml. Equivalent molecular weight : 756. Average particle size : 59 nm.
• a suspension of 75 g of N[1-phenyl-4-methyl-2-pyrazolin-5-one-yl(3')]methacrylamide in 200 ml of demineralized water wherein 5 g of the sodium salt of ⁇ -sulphopalmitic acid allyl ester had been dissolved was heated up to 70°C.
• To the suspension 6 g of butylacrylate were added and heating continued to 90°C.
• Thereupon 12.5 ml of a 1 % by weight aqueous polymerisation initiator solution of the sodium salt of 4,4'-azo- bis(4-cyanovaleric acid) were added and the temperature of 95°C was attained.
• the latex was concentrated by evaporation of some of the aqueous liquid. Yield : 500 ml of latex. Concentration of the copolymer in the latex : 18.2 g per 100 ml. Equivalent molecular weight : 898. Average particle size : 66 nm.
• the latex was concentrated by evaporation of some of the aqueous liquid. Yield : 464 ml of latex. Concentration of the copolymer in the latex : 18.1 g per 100 ml. Equivalent molecular weight : 708. Average particle size : 47 nm.
• the latices according to the invention may be incorporated in coating compositions for the manufacture of gelatin-containing layers of a photographic silver halide containing material.
• This layer may be a light-sensitive silver halide emulsion layer, or it may be a subbing layer, an antistress layer, an antihalation layer or any other auxiliary layer of the photographic element.
• the concentration of the latices may be adapted as desired. They are preferably prepared in such a way that the actual concentration of the copolymer in the latex is comprised between about 15 and 40 % by weight.
• the copolymer latices are mixed homogeneously in the desired amount with the aqueous gelatin-containing coating composition before coating.
• silver halide photographic materials In the preparation of silver halide photographic materials according to the present invention various silver halides can be used as light-sensitive substance. For instance silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide can be employed.
• silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide can be employed.
• the hydrophilic colloid used as the vehicle for the silver halide can be e.g. gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol or poly-N-vinyl pyrrolidone. If desired, compatible mixture of two or more of these colloids can be employed for dispersing the silver halide.
• the light-sensitive silver halide emulsions used in the preparation of a photographic material according to the present invention can be sensitized chemically as well as optically. They can be sensitized chemically by carrying out the ripening in the presence of small . amounts of sulphur-containing compounds such as allyl thiocyanate, allyl thiourea, or sodium thiosulphate.
• the emulsions can also be sensitized by means of reducing agents e.g.
• tin compounds as described in the French Patent Specification 1,146,955 and in Belgian Patent Specification 568,687, imino-aminomethane sulphinic acid compounds as described in United Kingdom Patent Specification 789)823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium, and rhodium compounds. They can be sensitized optically by means of organic sensitizing dyes known to those skilled in the art e.g. cyanine and merocyanine dyes.
• the said emulsions can also comprise compounds that sensitize the emulsions by development acceleration e.g. compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described i.a. in United States Patent Specifications 2,531,832; 2,533,990, in United Kingdom Patent Specifications 920,637 - 940,051 - 945,340 - 991,608 and 1,091,705 and onium derivatives of amino-N-oxides as described in United Kingdom Patent Specification 1,121,696.
• development acceleration e.g. compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described i.a. in United States Patent Specifications 2,531,832; 2,533,990, in United Kingdom Patent Specifications 920,637 - 940,051 - 945,340 - 991,608 and 1,091,705 and onium derivatives of amino-N-oxides as described in United Kingdom Patent Specification 1,121,696.
• the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-2-thione and 1-phenyl-2-tetrazdine-5-thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121 - 677,337, and in the United Kingdom Patent Specification 1,173,609.
• stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-2-thione and 1-phenyl-2-tetrazdine-5-thione and compounds of the hydroxytriazolopyrimidine type.
• mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121 - 677,337, and in the United Kingdom Patent Specification 1,173,609.
• the light-sensitive silver halide photographic materials incorporating at least one of the present copolymer latexes may comprise also any other kind of substance known in the art as ingredient for photographic silver halide materials e.g. plasticizers, hardening agents and/or wetting agents and other ingredients described for the preparation and composition of photographic silver halide materials in Research Disclosure No. 17,643 of December 1978.
• the coating of the aqueous hardening mixture may proceed onto an already dry silver halide emulsion layer or in a cascade-coating system simultaneously with the silver halide emulsion coating composition.
• concentration of applied hardening agents i.e. formaldehyde and phloroglucine depends on the gelatin content of the said colloid layer to be hardened and the thickness wherein the solution is applied. In a practically useful hardening agent solution the concentration of the formaldehyde is about 1 to 1.5 % by weight and of the phloroglucine about 0.5 % by weight.
• the total amount of applied hardening agents is normally in the range of 10 to 20 mmole of formaldehyde and 2 to 4 mmole of phloroglucinol per 100 g of gelatin.
• the non-diffuing colour couplers for each of the colour separation images are usually incorporated into the coating compositions of the differently sensitized silver halide emulsion layers.
• the non-diffusing colour couplers can also be added to the coating compositions of non-light-sensitive colloid layers that are in water-permeable relationship with the light-sensitive silver halide emulsion layers.
• a photographic multilayer colour material usually comprises a support, a red-sensitized silver halide emulsion layer with a cyan-forming colour coupler, a green- sensitized silver halide emulsion layer with a magenta-forming colour coupler, and a blue-sensitive silver halide emulsion layer with a yellow-forming colour coupler.
• non-migrating latex colour couplers can be incorporated in the coating composition of the silver halide emulsion layers or other colloid layers in water-permeable relationship therewith.
• the latex colour coupler Before addition of the latex colour coupler to the coating composition for the formation of a Layer e.g. silver halide emulsion layer of a photographic nultilayer colour material, the latex colour coupler can first be loaded with further couplers as referred to hereinbefore.
• Latex colour couplers according to the invention can be used in conjunction with various kinds of photographic emulsions.
• the latex couplers can be used in emulsions of the mixed packet type as described in the United States Patent Specification 2,698,794 or emulsions of the mixed grain type as described in the United States Patent Specification 2,592,243 or they can be used with silver halide emulsions of any type described in Research Disclosure 17,643 of December 1978 e.g. silver halide emulsions wherein latent images are formed predominantly at the surface of the silver halide crystal or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.
• the silver halide emulsions can be coated on a wide variety of supports.
• Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials, as well as paper and glass.
• the exposed silver halide is developed with an aromatic primary amino developing substance.
• All colour developing agents capable of forming azomethine dyes can be utilized as developers.
• Suitable developing agents are aromatic compounds such as p-phenylene diamines such as N,N-diethyl-p-phenylene diamine, N,N-dialkyl-N'- sulphomethyl-p-phenylene diamines and N,N-dialkyl-N'- carboxymethyl-p-phenylene diamines, and N,N-dialkyl-N'- carboxymethyl-p-phenylene diamines.
• 117 g of a silver bromoiodide emulsion (2.3 mole % of iodide) which comprises per kg an amount of silver halide equivalent to 47 g of silver nitrate and 73.4 g of gelatin, are diluted with 192.5 g of a 7.5 % aqueous solution of gelatin and 100 g of distilled water.
• To the emulsion obtained are added with stirring 12 ml of the latex prepared according to preparation 3b of United Kingdom Patent Specification No. 1,453,057 which corresponds to 0.006 mole of polymerised monomeric colour coupler.
• the common additives such as stabilizers, wetting agents and hardeners the necessary amount of distilled water is added to obtain 72 0 g .
• the emulsion obtained is coated on a cellulose triacetate support pro rata of 125 g per sq.m.
• the emulsion layer is dried and overcoated with a gelatin antistress layer.
• Material B, C and D were prepared in exactly the same way as material A except that instead of the latex prepared according to the said preparation 3b) of United Kingdom Patent Specification No. 1,453,057 14.1 ml of latex prepared according to preparation I (material B), 14.1 ml of latex prepared according to preparation II (material C) and 15.1 ml of latex prepared according to preparation III (material D) were used.
• the materials A to D were cut into strips and the resulting strips were exposed in a Herrnfeld sensitometer for 1/20th second through a continuous wedge with a constant of 0.30.
• the exposed strips were colour processed in the usual way, three different developers being used :

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• Materials Engineering (AREA)
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• 1980
  • 1980-09-18 DE DE8080200879T patent/DE3064831D1/de not_active Expired
  • 1980-09-18 EP EP80200879A patent/EP0027284B1/de not_active Expired
  • 1980-09-19 US US06/188,734 patent/US4340664A/en not_active Expired - Lifetime
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